Sulphonic compound



pertains moreparticularly tosulphonic acids and Patented Apr. 23,1935

,s ULrnomc e mtm Frederick H. "Manama,

Calumet City, Ills as signor to Standard Oil Company, Chicago, Ill.,

a-cornoration oi Indiana 5N0 Drawing.

' Application November 25, 16in, Serial No. 577,319 i 3 Claims. (!.260-159) 7 -'Ihisihvention-relates to sulphonic acids and it v w soaps prepared from particularly heavy'unsaturated hydrocarbons.

The object of my invention is to prepare sul ,phonic. compounds, either acidslor soaps, which are particularly suitableg forusie as wetting-agents, temulsion breakers, iat splittingagents,,soluble oils. textile oils, etc. "A iurtherobject is to utilize .by-products of petroleum refinin ;in}the preparation of. valuable sulphonic derivatives; 1 or 1 Other objects will be 'apparentias the detailed I description of myinvention proceeds.

I have discovered that heavy petroleum oils I dation' 1 or cracking are particularly susceptible to sulphonationjand that they yield sulphonic, compounds which'are exceptionally suitablev for the uses above stated. Preferred stocks arepressuretardistilla'te, pitch still distillate, andthe distillate obtained in" the destructive distillation of heavy residual oils' to form coke. The invention will be more clearly understood from thefollowing detaileddescription of preferred embodiment's.

Large amounts of gasolineVare-prepared by socalled cracking processes wherein heavier petroleum hydrocarbons such as gas oil are subjected to temperatures of about 850 to i900" F. underpressures of about"300 pounds, it being' understood, of course, that. these temperatures and. I pressures may vary within wide limits to fitjthe needsof petroleum cracking stocks and'to operate inflvapor phase or liquid phase to produce the desired end products. In all cracking processes, however, a part of the petroleum is converted into Lheavier products: these products may contain heavy unsaturated oils and tarry material and they are commonly called pressure tar. According to usual practice, the more volatile components thereof are evaporated and removed from the tar which is then useful for fuel, road oil; etc. On attempting to sulphonate this productwith strong or fuming sulphuric acid, only cokyproducts are obtained; together with copious quantities of sulphur dioxide gas; I have vfound, howeverz'that if this material is distilled, the distillate can be readily sulphonated to give good yields of sulphonic acids with very little formation of coky 50' matter. A distillate having an initial boiling point of about 450 F. or higher is particularly adaptable for the practice of my invention.

Pressure tar distillate having a boiling point above 450 F. may be sulphonated with fuming 104 /2% sulphuricacid, using about one to eight which have been subjected to a preliminary .oxi-

pounds of acid per gall'tin. I prefer, to maintain the temperature below 100 F.';. the temperature may be as high as 170 F. but high temperatures are likely to yield coke orundesirabie hard tarry products. The-heavy distillate from pressure tar 5 fmay be introducedinto a cooled mixer and the acid maybe added thereto with stirring at a rate sufficiently low to keep the temperature within the desired range.- I have found thatthere is an almost instantaneous reaction and that large yields of sulphonic compounds are obtained.

After the sulphonation I may steam the products to separate dilutesulphuric acid therefrom 'and thereby minimize the amount of salt formed by subsequent neutralization.

I then neutralize the acids with sodium hydroxide after which I extract with 50% alcohol. The products may bepurified by extracting with more concentrated alcohol or .in some cases the salts may be left in the soap to increase the efg0 fectiveness thereof. The soap may be dried to give a friable powder or flufiy mass which is hygroscopic and which has an alkaline reaction.

Instead of using a heavy distillate from pressure tar Imay use a heavy distillate from coking g5 stills producing coke by a cracking distillation of crude residuum. My invention makes use of the components having a boiling point above 450 F. or, in other words, I use the heavy unsaturated overhead products which are extensively cracked but'free from tarry material. This heavy overhead from the coker may besulphohated in the same manner as the overhead in the pressure distillate As another embodiment of my invention I may use the heavy unsaturated distillates obtained by reducing viscous residues to asphalt. When a petroleum oil is heated at high temperatures for the production of asphalt a certain amount of cracking takes place and I have discovered that 40 the unsaturated distillates boiling above 450 F. are particularly adaptable for sulphonation. As above described this distillate may be a traction of the so-calied pitch still distillate or it may be a fraction of the distillate from the oxidation of heavy residual oils at high temperatures to yield asphalt. The heavy distillates above described give unusually high yields 01 sulphonic compounds. For example, when an ordinary straight run distillate having an initial boiling point of about 450 F. is treated with fuming sulphuric acid only about 15% of sulphonic compounds are formed. When a pressure tar distillate of the same boiling range was sulphonated the yield of sulphonic compounds was Yields from 55 pitch distillate may be over 70% and the overhead from the coker likewise gives a very high yield.

It should be noted that my process completely eliminates coke and tarry material from the sulphonic compounds. This is extremely important,

- particularly in connection with the purification and separation of the sulphonic acid products.

While I have described preferred embodiments of my invention, it is understood that I do not limit myself to the treatment with 104%% sulphuric acid, and that variations in temperature, pressure, proportions, etc. may be made without departingfrom the invention. that chlorosulphonic acid may be used instead of fuming sulphuric acid and that the yields produced thereby are even higher than those pro-. duced by the sulphuric acid. Also I may ex- I tract the soaps or sulphonic compounds with chlorinated solventssuch as carbon tetrachloride, chloroform, etc. but alcohols are preferred.

The hydrocarbons which are sulphonated in accordance' with my invention may be characterized by the following properties Sulphuric acid absorption 12.6% to 20.0% Hexane solubility 99.8% to 100.0% Carbon residue 0.1% to 0.5%

As above stated, they give remarkable yields of sulphonic compounds having highly desirable properties. a

I claim: 1. The method of preparing sulphonic compounds which comprises heating a petroleum oil to about 850-900 F. to cause it to be cracked, separating from said cracked petroleum oil all components having a boiling point below 450 F.,

I have foundnents having a boiling point below 450 F., distilseparating from the remaining cracked petroleum composition all matter convertible into coke on sulphonation, leaving a clean unsaturated high boilinghydrocarbon oil characterized by a sulphuric acid absorption of about 12% to 20%, a hexane solubility of about 98.8% to and a carbon residue of about".1% to .5%, and sulphcnating said clean unsaturated high boiling hydrocarbon oil.

2. The method oi preparing sulphonic compounds which comprises heating a petroleum oil to a cracking temperatur'e'to cause the formation of unsaturated hydrocarbons and tarry matter, separating from said heated mixture all compoling the remaining components to remove clean unsaturated high boiling hydrocarbons from tarry, asphaltic and coke-forming materials, and sulphonating the distillate which is characterized by an initial boiling point of at least 450 F., by a sulphuric acid absorptionpi' at least 12%, a hexane solubility of at least 99.8%, and acarbon residue of less than .5'%.

3. The method of preparing sulphonic compounds which comprises heating a petroleum oil to about 850-900 F. whereby the oil is cracked and gasoline, gas oil and pressure tar are formed, separating the gasoline and gas oil from said pressure tar, distilling from said pressure tar all material having products boiling below 450 F., subsequently distilling from said pressure tar a high boiling unsaturated hydrocarbon oil which is substantially free from matter convertible to coke on sulphonation, and sulphonating said heavy pressure tar distillate.-

FREDERICK H. MACLAREN. 

